Heterocyclic-amide catalyst compositions for the polymerization of olefins

ABSTRACT

A family of novel hetrocyclic-amide type catalyst precursors useful for the polymerization of olefins, such as ethylene, higher alpha-olefins, dienes, and mixtures thereof.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a Continuation Application of, and claimspriority to U.S. Ser. No. 10/023,256 filed Dec. 18, 2001, now issued asU.S. Pat. No. 6,864,205, and is herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a family of novel heterocyclic-amidetype catalyst precursors useful for the polymerization of olefins, suchas ethylene, higher alpha-olefins, dienes, or other monomers andmixtures thereof.

BACKGROUND OF THE INVENTION

A variety of metallocenes and other single site-like catalysts have beendeveloped to prepare olefin polymers. Metallocenes are organometalliccoordination complexes containing one or more pi-bonded moieties (i.e.,cyclopentadienyl groups) in association with a metal atom. Catalystcompositions containing metallocenes and other single site-likecatalysts are highly useful for the preparation of polyolefins,producing relatively homogeneous copolymers at excellent polymerizationrates while allowing one to closely tailor the final properties of thepolymer as desired.

Recently, work relating to certain nitrogen-containing, single site-likecatalyst precursors has been published. For example, PCT application No.WO 96/23101 relates to di(imine) metal complexes that are transitionmetal complexes of bidentate ligands selected from the group consistingof:

-   wherein said transition metal is selected from the group consisting    of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni, and Pd;-   R² and R⁵ are each independently hydrocarbyl or substituted    hydrocarbyl, provided that the carbon atom bound to the imino    nitrogen atom has at least two carbon atoms bound to it;-   R³ and R⁴ are each independently, hydrogen, hydrocarbyl, substituted    hydrocarbyl, or R³ and R⁴ taken together are hydrocarbylene or    substituted hydrocarbylene to form a carbocyclic ring;-   R⁴⁴ is a hydrocarbyl or substituted hydrocarbyl, and R²⁸ is    hydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁴ and R²⁸    taken together form a ring;-   R⁴⁵ is a hydrocarbyl or substituted hydrocarbyl, and R²⁹ is    hydrogen, hydrocarbyl or substituted hydrocarbyl or R⁴⁵ and R²⁹    taken together form a ring;-   each R³⁰ is independently hydrogen, hydrocarbyl or substituted    hydrocarbyl, or two of R³⁰ taken together form a ring;-   each R³¹ is independently hydrogen, hydrocarbyl or substituted    hydrocarbyl;-   R⁴⁶ and R⁴⁷ are each independently hydrocarbyl or substituted    hydrocarbyl, provided that the carbon atom bound to the imino    nitrogen atom has at least two carbon atoms bound to it;-   R⁴⁸ and R⁴⁹ are each independently hydrogen, hydrocarbyl, or    substituted hydrocarbyl;-   R²⁰ and R²³ are each independently hydrocarbyl, or substituted    hydrocarbyl;-   R²¹ and R²² are independently hydrogen, hydrocarbyl, or substituted    hydrocarbyl; and-   n is 2 or 3;-   and provided that:-   the transition metal also has bonded to it a ligand that may be    displaced by or added to the olefin monomer being polymerized; and-   when the transition metal is Pd, said bidentate ligand is (V), (VII)    or (VIII).

Also, U.S. Pat. No. 6,096,676, which is incorporated herein byreference, teaches a catalyst precursor having the formula:

-   wherein M is a Group IVB metal;-   each L is a monovalent, bivalent, or trivalent anion;-   X and Y are each heteroatoms, such as nitrogen;-   each cyclo is a cyclic moiety;-   each R¹ is a group containing 1 to 50 atoms selected from the group    consisting of hydrogen and Group IIIA to Group VIIA elements, and    two or more adjacent R¹ groups may be joined to form a cyclic    moiety;-   each R² is a group containing 1 to 50 atoms selected from the group    consisting of hydrogen and Group IIIA to Group VIIA elements and two    or more adjacent R² groups may be joined to form a cyclic moiety;-   W is a bridging group; and-   each m is independently an integer from 0 to 5.

Also taught is a catalyst composition comprising this catalyst precursorand an activating co-catalyst, as well as a process for thepolymerization of olefins using this catalyst composition.

Although there are a variety of single site catalysts taught in theprior art, some of which are commercially available, there still exist aneed in the art for improved catalysts and catalyst precursors that arecapable of producing polyolefins having predetermined properties.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided catalystprecursors that contain the grouping:

wherein one heteroatom (J) is part of a ring structure and the other (X)is not. The most preferred heteroatom catalyst precursors are thosewherein the heteroatom-containing ring moiety is a pyrrole or apiperidine and wherein the non-ring structure heteroatom moiety is anamide or amido group when Y is nitrogen and a phosphide or phosphidogroup when Y is phosphorus.

The catalyst precursors of the present invention can be represented by aformula selected from the following Group A formulae, Group B formulae,or Group C formulae.

-   where a is an integer from 1 to 5;-   T is a chemical moiety having one or more, preferably 1 to 100    atoms, which can include hydrogen when a=1, and T is a bridging    group that bridges the Y atoms when a=2 to 5;-   M is a metallic element selected from Groups 1 to 15, and the    Lanthanide series of the Periodic Table of the Elements;-   Z is a coordination ligand;-   m is an integer from 1 to 3;-   each L is a monovalent, bivalent, or trivalent anionic ligand;-   n is an integer from 1 to 6;-   m is an integer from 0 to 5;-   Y is a heteroatom selected from nitrogen, oxygen, sulfur, and    phosphorus;-   J is a heteroatom that is part of a ring structure and is selected    from nitrogen, oxygen, sulfur, and phosphorus;-   R can be independently hydrogen, or a non-bulky or a bulky    substituent. If it is independently a non-bulky substituent it will    have relatively low steric hindrance with respect to Y, and it is    preferably a C₁ to C₂₀ alkyl group, preferably a primary alkyl    group. Low steric hindrance, as used herein means that the non-bulky    R group has no branching within 3 atoms of Y.    If R is independently a bulky group it will have a relatively large    steric hindrance with respect to Y, and it will preferably be    selected from alkyl (preferably branched), alkenyl (preferably    branched), cycloalkyl, heterocyclic (both heteroalkyl and    heteroaryl), aryl, alkylaryl, arylalkyl, and polymeric, including    metallorganics such as the P-N ring structures set forth below and    inorganic-organic hybrid structures, also such as those set forth    below. It is preferred that R, when bulky, contain from about 3 to    50, more preferably from about 3 to 30 non-hydrogen atoms, and most    preferably from about 2 to 20 atoms. Also, one or more of the carbon    or hydrogen positions can be substituted with an element other than    carbon and hydrogen, preferably an element selected from Groups 14    to 17, more preferably a Group 14 element such as silicon, a Group    15 element such as nitrogen, a Group 16 element such as oxygen, or a    Group 17 halogen. b is an integer from 0 to 20.

where T is a bridging group containing one or more bridging atoms andwherein Y, M, L, Z, R, b, n, m, and a are as defined above for the GroupA formulae.

BRIEF DESCRIPTION OF THE FIGURE

The sole FIGURE hereof shows two plots of molecular weight distributionas a function of the log of molecular weight, as measured by sizeexclusion chromatography, using the amine derived from the alkylation of2-acetylpyridine(1-amino-cis-2,6-dimethyl piperidine)imine withtetrabenzyl zirconium. One plot represents the catalyst containing 0.5micromoles of Zr and the other represents the catalyst containing 2.0micromoles of Zr.

DETAILED DESCRIPTION OF THE INVENTION

As previously mentioned the present invention relates to catalystprecursors that contain the grouping:

wherein one heteroatom (J) is part of a ring structure and the other (Y)is not. As mentioned above, the most preferred heteroatom catalystprecursors are those wherein the heteroatom-containing ring moiety is apyrrole or a piperidine and wherein the non-ring structure heteroatommoiety is an amide or amido group when Y is nitrogen and a phosphide orphosphido group when Y is phosphorus.

The catalyst precursors of the present invention can be any of thoserepresented by any of the following formulae.

-   wherein a is an integer from 1 to 5;-   T is a chemical moiety having one or more, preferably 1 to 100    atoms, which can include hydrogen when a=1, and T is a bridging    group that bridges the Y atoms when a=2 to 5;

wherein for the Group B and Group C formulae T is a bridging moiety forbridging Y and M.

M is a metallic element selected from Groups 1 to 15, preferably fromGroups 3 to 13 elements, more preferably the transition metals fromGroups 3 to 7, and the Lanthanide series of the Periodic Table of theElements. The Periodic Table of the Elements referred to herein is thattable that appears in the inside front cover of Lange's Handbook ofChemistry, 15^(th) Edition, 1999, McGraw Hill Handbooks.

Z is a coordination ligand. Preferred coordination ligands includetriphenylphosphine, tris(C₁–C₆ alkyl) phosphine, tricycloalkyl phophine,diphenyl alkyl phosphine, dialkyl phenyl phosphine, trialkylamine,arylamine such as pyridine, substituted or unsubstituted C₂ to C₂₀alkenes (e.g. ethylene, propylene, butene, hexane, octane, decene,dodecene, allyl, and the like) in which the substituent is a halogenatom (preferably chloro), an ester group, a C₁ to C₄ alkoxy group, anamine group (—NR₂ where each R individually is a C₁ to C₃ alkyl),carboxylic acid, alkali metal salt, di(C₁ to C₄) alkyl ether,tetrahydrofuran (THF), a nitrile such a acetonitrile, an η⁴-diene, andthe like.

Each L is a monovalent, bivalent, or trivalent anionic ligand,preferably containing from about 1 to 50 non-hydrogen atoms, morepreferably from about 1 to 20 non-hydrogen atoms and is independentlyselected from the group consisting of halogen containing groups;hydrogen; alkyl; aryl; alkenyl; alkylaryl; arylalkyl; hydrocarboxy;amides, phosphides; sulfides; silyalkyls; diketones; borohydrides; andcarboxylates. More preferred are alkyl, arylalkyl, and halogencontaining groups.

n is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3.

Y is a heteroatom selected from nitrogen, oxygen, sulfur, andphosphorus, preferably selected from nitrogen and phosphorus, and morepreferably nitrogen.

J is a heteroatom that is part of a ring structure, which heteroatom isselected from the group consisting of nitrogen, oxygen, sulfur, andphosphorus; preferably nitrogen and phosphorus, and more preferablynitrogen.

It is preferred that the ring be a five or six member ring, morepreferably a pyrrole or a piperidine ring structure.

R can be a non-bulky substituent or a bulky substituent. By a non-bulkysubstituent we mean that it has relatively low steric hindrance withrespect to Y. Non-limiting examples of non-bulky substituents includestraight and branched chain alkyl groups, preferably straight chaingroups. R is also preferably a C₁ to C₃₀ alkyl group, more preferably aC₁ to C₂₀ alkyl group, and most preferably and n-octyl group. If thenon-bulky group is branched, the branch point must be at least 3 atomsremoved from Y.

R can also be a bulky substituent. By bulky substituent we mean that Rwill be sterically hindering with respect to Y. When R is a bulkysubstituent it can be selected from alkyl, alkenyl, cycloalkyl,heterocyclic (both heteroalkyl and heteroaryl), alkylaryl, arylalkyl,and polymeric, including inorganics such as the P-N ring structures setforth below and inorganic-organic hybrid structures, such as those setforth below. It is preferred that the R substituent contain from about 1to 50, more preferably from about 1 to 20 non-hydrogen atoms. Also, oneor more of the carbon or hydrogen positions may be substituted with anelement other than carbon and hydrogen, preferably an element selectedfrom Groups 14 to 17, more preferably a Group 14 element such assilicon, a Group 15 element such as nitrogen, a Group 16 element such asoxygen, or a Group 17 halogen.

When a=2, that is when there are two Y atoms, preferred T groups thatcan be used for Group C formulae compositions are selected from:

The following T groups can also be used when a=2, for compositionsrepresented by Group A formulae:

wherein the Y atoms are provided for convenience and are not part of theT moiety.

When a=1, that is when there is only one Y atom, preferred T groups thatcan be used for those compositions represented by Group A formulainclude:

The following are preferred T groups when a=2 for compositionsrepresented by Group A formulae:

The Y substituents are included for convenience.

Non-limiting examples of the ring structure include:

The catalyst precursors can be prepared by any suitable synthesis methodand the method of synthesis is not critical to the present invention.One useful method of preparing the catalyst precursors of the presentinvention is by reacting a suitable metal compound, preferably onehaving a displaceable anionic ligand, with a heteroatom-containingligand of this invention. Non-limiting examples of suitable metalcompounds include organometallics, metal halides, sulfonates,carboxylates, phosphates, organoborates (including fluoro-containing andother subclasses), acetonacetonates, sulfides, sulfates,tetrafluoroborates, nitrates, perchlorates, phenoxides, alkoxides,silicates, arsenates, borohydrides, naphthenates, cyclooctadienes, dieneconjugated complexes, thiocyanates, cyanates, and the metal cyanides.Preferred are the organometallics and the metal halides. More preferredare the organometallics.

As previously mentioned, the metal of the organometal compound may beselected from Groups 1 to 16, preferably it is a transition metalselected from Groups 3 to 13 elements and Lanthanide series elements. Itis also preferred that the metal be selected from Groups 3 to 7elements. The groups referred to are from the Periodic Table of theElements. It is particularly preferred that the metal be a Group 4metal, more particularly preferred is zirconium and hafnium, and mostparticularly preferred is zirconium.

The transition metal compound can, for example, be a metal hydrocarbylsuch as: a metal alkyl, a metal aryl, a metal arylalkyl; a metalsilylalkyl; a metal diene, a metal amide; or a metal phosphide.Preferably, the transition metal compound is a zirconium or hafniumhydrocarbyl. More preferably, the transition metal compound is azirconium arylalkyl. Most preferably, the transition metal compound istetrabenzylzirconium.

Examples of useful and preferred transition metal compounds include:

-   -   (i) tetramethylzirconium, tetraethylzirconium,        zirconiumdichloride (η⁴-1,4-diphenyl-1,3-butadiene), bis        (triethylphosphine) and zirconiumdichloride        (η⁴-1,4-diphenyl-1,3-butadiene) bis (tri-n-propylphosphine).        tetrakis[trimethylsilylmethyl]zirconium, tetrakis        [dimethylamino]zirconium, dichlorodibenzylzirconium,        chlorotribenzylzirconium, trichlorobenzylzirconium,        bis[dimethylamino]bis[benzyl]zirconium, and        tetrabenzylzirconium;    -   (ii) tetramethyltitanium. Tetramethyltitanium.        titaniumdichloride (η⁴-1,4-diphenyl-1,3-butadiene), bis        (triethylphosphine) and titaniumdichloride        (η⁴-1,4-diphenyl-1,3-butadiene) bis (tri-n-propylphosphine),        tetrakis[trimethylsilylmethyl]-titanium,        tetrakis[dimethylamino]titanium, dichlorodibenzyltitanium,        chlorotribenzyltitanium, trichlorobenzyltitanium,        bis[dimethylamino]bis[benzyl]titanium, and tetrabenzyltitanium;        and    -   (iii) tetramethylhafnium, tetraethylhafnium, hafniumdichloride        (η⁴-1,4-diphenyl-1,3-butadiene), bis (triethylphosphine) and        hafniumdichloride (η⁴-1,4-diphenyl-1,3-butadiene) bis        (tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]hafnium,        tetrakis[dimethylamino]hafnium, dichlorodibenzylhafnium,        chlorotribenzylhafnium, trichlorobenzylhafnium,        bis[dimethylamino]bis[benzyl]hafnium, and tetrabenzylhafnium.

One preferred heteroatom-containing ligand that can be used in thepractice of the present invention is:

The imine of 2-acetylpyridine is first synthesized.

Reaction of the 2-acetylpyridine imine with tetrabenzyl zirconium willlead to the products shown below.

Activators and Activation Methods for Catalyst Compounds

The polymerization catalyst compounds of the invention are typicallyactivated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts.

A. Alumoxane and Aluminum Alkyl Activators

In one embodiment, alumoxanes activators are utilized as an activator inthe catalyst composition of the invention. Alumoxanes are generallyoligomeric compounds containing —Al(R)—O— subunits, where R is an alkylgroup. Examples of alumoxanes include methylalumoxane (MAO), modifiedmethylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alumoxanesmay be produced by the hydrolysis of the respective trialkylaluminumcompound. MMAO may be produced by the hydrolysis of trimethylaluminumand a higher trialkylaluminum such as triisobutylaluminum. MMAO's aregenerally more soluble in aliphatic solvents and more stable duringstorage. There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166,5,856,256 and 5,939,346 and European publications EP-A-0 561 476,EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCTpublications WO 94/10180 and WO 99/15534, all of which are herein fullyincorporated by reference. A another alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,covered under U.S. Pat. No. 5,041,584).

Aluminum Alkyl or organoaluminum compounds which may be utilized asactivators include trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

B. Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, thallium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, napthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is trisperfluorophenyl boron ortrisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L-H)_(d) ⁺(A^(d−))

-   -   wherein L is an neutral Lewis base;    -   H is hydrogen;    -   (L-H)⁺ is a Bronsted acid;    -   A^(d−) is a non-coordinating anion having the charge d−;    -   d is an integer from 1 to 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from thebulky ligand metallocene or Group 15 containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andmixtures thereof. The activating cation (L-H)_(d) ⁺ may also be anabstracting moiety such as silver, carboniums, tropylium, carbeniums,ferroceniums and mixtures, preferably carboniums and ferroceniums. Mostpreferably (L-H)_(d) ⁺ is triphenyl carbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2–6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺ (A^(d−))is N,N-dimethylanilinium tetra(perfluorophenyl)borate ortriphenylcarbenium tetra(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP-A-0 426 637, EP-A-0 573 403 andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

Supports, Carriers and General Supporting Techniques

Although not preferred, the catalyst system of the invention can includea support material or carrier, or a supported activator. For example,the catalyst compound of the invention can be deposited on, contactedwith, vaporized with, bonded to, or incorporated within, adsorbed orabsorbed in, or on, a support or carrier.

A. Support Material

The support material, if used, can be any of the conventional supportmaterials. Preferably the supported material is a porous supportmaterial, for example, talc, inorganic oxides and inorganic chlorides.Other support materials include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene polyolefins or polymeric compounds,zeolites, clays, or any other organic or inorganic support material andthe like, or mixtures thereof.

The preferred support materials are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, fumed silica, alumina (WO 99/60033), silica-alumina and mixturesthereof. Other useful supports include magnesia, titania, zirconia,magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EuropeanPatent EP-B 1 0 511 665), phyllosilicate, zeolites, talc, clays (U.S.Pat. No. 6,034,187) and the like. Also, combinations of these supportmaterials may be used, for example, silica-chromium, silica-alumina,silica-titania and the like. Additional support materials may includethose porous acrylic polymers described in EP 0 767 184 B 1, which isincorporated herein by reference. Other support materials includenanocomposites as described in PCT WO 99/47598, aerogels as described inWO 99/48605, spherulites as described in U.S. Pat. No. 5,972,510 andpolymeric beads as described in WO 99/50311, which are all hereinincorporated by reference. A preferred support is fumed silica availableunder the trade name Cabosil™ TS-610, available from Cabot Corporation.Fumed silica is typically a silica with particles 7 to 30 nanometers insize that has been treated with dimethylsilyldichloride such that amajority of the surface hydroxyl groups are capped.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeis from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 μm. Theaverage pore size of the carrier of the invention typically has poresize in the range of from 10 to 1000 Å, preferably 50 to about 500 Å,and most preferably 75 to about 350 Å.

The support materials may be treated chemically, for example with afluoride compound as described in WO 00/12565, which is hereinincorporated by reference. Other supported activators are described infor example WO 00/13792 that refers to supported boron containing solidacid complex.

In a preferred method of forming a supported catalyst compositioncomponent, the amount of liquid in which the activator is present is inan amount that is less than four times the pore volume of the supportmaterial, more preferably less than three times, even more preferablyless than two times; preferred ranges being from 1.1 times to 3.5 timesrange and most preferably in the 1.2 to 3 times range. In an alternativeembodiment, the amount of liquid in which the activator is present isfrom one to less than one times the pore volume of the support materialutilized in forming the supported activator.

Procedures for measuring the total pore volume of a porous support arewell known in the art. Details of one of these procedures is discussedin Volume 1, Experimental Methods in Catalytic Research (Academic Press,1968) (specifically see pages 67–96). This preferred procedure involvesthe use of a classical BET apparatus for nitrogen absorption. Anothermethod well known in the art is described in Innes, Total Porosity andParticle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3,Analytical Chemistry 332–334 (March, 1956).

B. Supported Activators

In one embodiment, the catalyst composition includes a supportedactivator. Many supported activators are described in various patentsand publications which include: U.S. Pat. No. 5,728,855 directed to theforming a supported oligomeric alkylaluminoxane formed by treating atrialkylaluminum with carbon dioxide prior to hydrolysis; U.S. Pat. Nos.5,831,109 and 5,777,143 discusses a supported methylalumoxane made usinga non-hydrolytic process; U.S. Pat. No. 5,731,451 relates to a processfor making a supported alumoxane by oxygenation with a trialkylsiloxymoiety; U.S. Pat. No. 5,856,255 discusses forming a supported auxiliarycatalyst (alumoxane or organoboron compound) at elevated temperaturesand pressures; U.S. Pat. No. 5,739,368 discusses a process of heattreating alumoxane and placing it on a support; EP-A-0 545 152 relatesto adding a metallocene to a supported alumoxane and adding moremethylalumoxane; U.S. Pat. Nos. 5,756,416 and 6,028,151 discuss acatalyst composition of a alumoxane impregnated support and ametallocene and a bulky aluminum alkyl and methylalumoxane; EP-B 1-0 662979 discusses the use of a metallocene with a catalyst support of silicareacted with alumoxane; PCT WO 96/16092 relates to a heated supporttreated with alumoxane and washing to remove unfixed alumoxane; U.S.Pat. Nos. 4,912,075, 4,937,301, 5,008,228, 5,086,025, 5,147,949,4,871,705, 5,229,478, 4,935,397, 4,937,217 and 5,057,475, and PCT WO94/26793 all directed to adding a metallocene to a supported activator;U.S. Pat. No. 5,902,766 relates to a supported activator having aspecified distribution of alumoxane on the silica particles; U.S. Pat.No. 5,468,702 relates to aging a supported activator and adding ametallocene; U.S. Pat. No. 5,968,864 discusses treating a solid withalumoxane and introducing a metallocene; EP 0 747 430 A1 relates to aprocess using a metallocene on a supported methylalumoxane andtrimethylaluminum; EP 0 969 019 A1 discusses the use of a metalloceneand a supported activator; EP-B2-0 170 059 relates to a polymerizationprocess using a metallocene and a organo-aluminuim compound, which isformed by reacting aluminum trialkyl with a water containing support;U.S. Pat. No. 5,212,232 discusses the use of a supported alumoxane and ametallocene for producing styrene based polymers; U.S. Pat. No.5,026,797 discusses a polymerization process using a solid component ofa zirconium compound and a water-insoluble porous inorganic oxidepreliminarily treated with alumoxane; U.S. Pat. No. 5,910,463 relates toa process for preparing a catalyst support by combining a dehydratedsupport material, an alumoxane and a polyfunctional organic crosslinker;U.S. Pat. Nos. 5,332,706, 5,473,028, 5,602,067 and 5,420,220 discusses aprocess for making a supported activator where the volume of alumoxanesolution is less than the pore volume of the support material; WO98/02246 discusses silica treated with a solution containing a source ofaluminum and a metallocene; WO 99/03580 relates to the use of asupported alumoxane and a metallocene; EP-A1-0 953 581 discloses aheterogeneous catalytic system of a supported alumoxane and ametallocene; U.S. Pat. No. 5,015,749 discusses a process for preparing apolyhydrocarbyl-alumoxane using a porous organic or inorganic imbibermaterial; U.S. Pat. Nos. 5,446,001 and 5,534,474 relates to a processfor preparing one or more alkylaluminoxanes immobilized on a solid,particulate inert support; and EP-A1-0 819 706 relates to a process forpreparing a solid silica treated with alumoxane. Also, the followingarticles, also fully incorporated herein by reference for purposes ofdisclosing useful supported activators and methods for theirpreparation, include: W. Kaminsky, et al., “Polymerization of Styrenewith Supported Half-Sandwich Complexes”, Journal of Polymer Science Vol.37, 2959–2968 (1999) describes a process of adsorbing a methylalumoxaneto a support followed by the adsorption of a metallocene; Junting Xu, etal. “Characterization of isotactic polypropylene prepared withdimethylsilyl bis(1-indenyl)zirconium dichloride supported onmethylaluminoxane pretreated silica”, European Polymer Journal 35 (1999)1289–1294, discusses the use of silica treated with methylalumoxane anda metallocene; Stephen O'Brien, et al., “EXAFS analysis of a chiralalkene polymerization catalyst incorporated in the mesoporous silicateMCM-41” Chem. Commun. 1905–1906 (1997) discloses an immobilizedalumoxane on a modified mesoporous silica; and F. Bonini, et al.,“Propylene Polymerization through Supported Metallocene/MAO Catalysts:Kinetic Analysis and Modeling” Journal of Polymer Science, Vol. 332393–2402 (1995) discusses using a methylalumoxane supported silica witha metallocene. Any of the methods discussed in these references areuseful for producing the supported activator component utilized in thecatalyst composition of the invention and all are incorporated herein byreference.

In another embodiment, the supported activator, such as supportedalumoxane, is aged for a period of time prior to use herein. Forreference please refer to U.S. Pat. Nos. 5,468,702 and 5,602,217,incorporated herein by reference.

In an embodiment, the supported activator is in a dried state or asolid. In another embodiment, the supported activator is in asubstantially dry state or a slurry, preferably in a mineral oil slurry.

In another embodiment, two or more separately supported activators areused, or alternatively, two or more different activators on a singlesupport are used.

In another embodiment, the support material, preferably partially ortotally dehydrated support material, preferably 200° C. to 600° C.dehydrated silica, is then contacted with an organoaluminum or alumoxanecompound. Preferably in an embodiment where an organoaluminum compoundis used, the activator is formed in situ on and in the support materialas a result of the reaction of, for example, trimethylaluminum andwater.

In another embodiment, Lewis base-containing supports are reacted with aLewis acidic activator to form a support bonded Lewis acid compound. TheLewis base hydroxyl groups of silica are exemplary of metal/metalloidoxides where this method of bonding to a support occurs. This embodimentis described in U.S. patent application Ser. No. 09/191,922, filed Nov.13, 1998, which is herein incorporated by reference.

Other embodiments of supporting an activator are described in U.S. Pat.No. 5,427,991, where supported non-coordinating anions derived fromtrisperfluorophenyl boron are described; U.S. Pat. No. 5,643,847discusses the reaction of Group 13 Lewis acid compounds with metaloxides such as silica and illustrates the reaction oftrisperfluorophenyl boron with silanol groups (the hydroxyl groups ofsilicon) resulting in bound anions capable of protonating transitionmetal organometallic catalyst compounds to form catalytically activecations counter-balanced by the bound anions; immobilized Group IIIALewis acid catalysts suitable for carbocationic polymerizations aredescribed in U.S. Pat. No. 5,288,677; and James C. W. Chien, Jour. Poly.Sci.: Pt A: Poly. Chem, Vol. 29, 1603–1607 (1991), describes the olefinpolymerization utility of methylalumoxane (MAO) reacted with silica(SiO₂) and metallocenes and describes a covalent bonding of the aluminumatom to the silica through an oxygen atom in the surface hydroxyl groupsof the silica.

In a preferred embodiment, a supported activator is formed by preparingin an agitated, and temperature and pressure controlled vessel asolution of the activator and a suitable solvent, then adding thesupport material at temperatures from 0° C. to 100° C., contacting thesupport with the activator solution for up to 24 hours, then using acombination of heat and pressure to remove the solvent to produce a freeflowing powder. Temperatures can range from 40 to 120° C. and pressuresfrom 5 psia to 20 psia (34.5 to 138 kPa). An inert gas sweep can also beused in assist in removing solvent. Alternate orders of addition, suchas slurrying the support material in an appropriate solvent then addingthe activator, can be used.

Polymerization Process

The catalyst systems prepared and the method of catalyst system additiondescribed above are suitable for use in any prepolymerization and/orpolymerization process over a wide range of temperatures and pressures.The temperatures may be in the range of from −60° C. to about 280° C.,preferably from 50° C. to about 200° C., and the pressures employed maybe in the range from 1 atmosphere to about 500 atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof. Particularly preferredis a gas phase or slurry phase polymerization of one or more olefins atleast one of which is ethylene or propylene.

In one embodiment, the process of this invention is directed toward asolution, high pressure, slurry or gas phase polymerization process ofone or more olefin monomers having from 2 to 30 carbon atoms, preferably2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Theinvention is particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 3 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

In an embodiment, the mole ratio of comonomer to ethylene, C_(X)/C₂,where C_(X) is the amount of comonomer and C₂ is the amount of ethyleneis between about 0.001 to 0.200 and more preferably between about 0.002to 0.008.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene catalysts as described in U.S. Pat.Nos. 5,296,434 and 5,278,264, both of which are herein incorporated byreference.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 600 psig (4138 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

Other gas phase processes contemplated by the process of the inventioninclude series or multistage polymerization processes. Also gas phaseprocesses contemplated by the invention include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all ofwhich are herein fully incorporated by reference.

In a preferred embodiment, the reactor utilized in the present inventionis capable of and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is referred to asa particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. Nos. 4,613,484 and5,986,021, which are herein fully incorporated by reference.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr). Examples of solutionprocesses are described in U.S. Pat. Nos. 4,271,060, 5,001,205,5,236,998, 5,589,555 and 5,977,251 and PCT WO 99/32525 and PCT WO99/40130, which are fully incorporated herein by reference

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the presence of a bulkyligand metallocene catalyst system of the invention and in the absenceof or essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. Nos.5,712,352 and 5,763,543, which are herein fully incorporated byreference.

In one embodiment of the invention, olefin(s), preferably C₂ to C₃₀olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of themetallocene catalyst systems of the invention described above prior tothe main polymerization. The prepolymerization can be carried outbatchwise or continuously in gas, solution or slurry phase including atelevated pressures. The prepolymerization can take place with any olefinmonomer or combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference.

In one embodiment, toluene is not used in the preparation orpolymerization process of this invention.

Polymer Products

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedby the process of the invention include linear low density polyethylene,elastomers, plastomers, high density polyethylenes, medium densitypolyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers. Also produced are isotatic polymers, such aspoly-1-hexene and bimodal polyethylene.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/ccto 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

The polymers produced by the process of the invention typically have amolecular weight distribution, a weight average molecular weight tonumber average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 30, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

Also, the polymers of the invention typically have a narrow compositiondistribution as measured by Composition Distribution Breadth Index(CDBI). Further details of determining the CDBI of a copolymer are knownto those skilled in the art. See, for example, PCT Pat. Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference.

The polymers of the invention in one embodiment have CDBI's generally inthe range of greater than 50% to 100%, preferably 99%, preferably in therange of 55% to 85%, and more preferably 60% to 80%, even morepreferably greater than 60%, still even more preferably greater than65%.

In another embodiment, polymers produced using a catalyst system of theinvention have a CDBI less than 50%, more preferably less than 40%, andmost preferably less than 30%.

The polymers of the present invention in one embodiment have a meltindex (MI) or (I₂) as measured by ASTM-D-1238-E in the range from nomeasurable flow to 1000 dg/min, more preferably from about 0.01 dg/minto about 100 dg/min, even more preferably from about 0.1 dg/min to about50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

The polymers of the invention in an embodiment have a melt index ratio(I₂₁/I₂) (₂₁ is measured by ASTM-D-1238-F) of from 10 to less than 25,more preferably from about 15 to less than 25.

The polymers of the invention in a preferred embodiment have a meltindex ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1 238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

In yet another embodiment, propylene based polymers are produced in theprocess of the invention. These polymers include atactic polypropylene,isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.Other propylene polymers include propylene block or impact copolymers.Propylene polymers of these types are well known in the art see forexample U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and5,459,117, all of which are herein incorporated by reference.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes, elastomers, plastomers, high pressure lowdensity polyethylene, high density polyethylenes, polypropylenes and thelike.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, pipe, geomembranes, and pondliners. Molded articles include single and multi-layered constructionsin the form of bottles, tanks, large hollow articles, rigid foodcontainers and toys, etc.

The present invention will be illustrated in more detail with referenceto the following examples, which should not be construed to be limitingin scope of the present invention.

GLOSSARY

Activity is measured in g of polyethylene/mmol of metal per hr at 100psig ethylene.

I2 is the flow index (dg/min) as measured by ASTM D-1238-Condition E at190° C.

I21 is the flow index (dg/min) as measured by ASTM D-1238-Condition F.

MFR is the Melt Flow Ratio, I21/I2.

MMAO is a solution of modified methylalumoxane in heptane, approximately1.9 molar in aluminum, commercially available from Akzo Chemicals, Inc.(type 3).

BBF is Butyl Branching Frequency, number of butyl branches per 1000 mainchain carbon atoms, as determined by infrared measurement techniques.

M_(w) is Weight Average Molecular Weight, as determined by gelpermeation chromatography using crosslinked polystyrene columns; poresize sequence: 1 column less than 1000 Å, 3 columns of mixed 5×10⁷ Å;1,2,4-trichlorobenzene solvent at 140° C., with refractive indexdetection. M_(n) is number average molecular weight.

PDI is the Polydispersity Index, equivalent to Molecular WeightDistribution (M_(w)/M_(n)).

EXAMPLES

Synthesis of 2-Acetylpyridine hydrazine Adduct and2-Acetylpyridine{N-1-2,5 dimethylpyrrole}imine

General procedure: 2-Acetylpyridine (5.0 g, 41.3 mmol) was charged to aflask equipped with a stir bar. Hydrazine (1.33 g, 41.3 mmol) was addeddropwise to the stirring 2-acetylpyridine. The exothermic reaction wasallowed to cool to room temperature and solidify. The solids werereacted with acetonyl acetone (1 equivalent, 2 equivalents and 10equivalents) in three separate reaction with hydrochloric acid (1equivalent) in ether solvent. The reaction was heated to 60° C. Theproduct was isolated.

Reaction of N-PyrrolImine Ligand with Tetrabenzyl zirconium

General procedure: In dry the box tetrabenzyl zirconium (0.200 mmol,0.091 g) was charged to a 7 mL amber bottle equipped with a stir bar andcap. Benzene-d₆ (1.5 mL) was added and stirred to dissolve. To a vialwas charged N-pyrrolimine ligand (0.200 mmol, 0.042 g) and 1.5 mLBenzene-d₆. The ligand solution was transferred into the tetrabenzylzirconium solution.

NMR analysis revealed (Composition 45% complex, 55%tetrabenzylzirconium).

This complex exhibited ethylene polymerization activity in a slurryreactor with modified methylalumoxane cocatalyst. This result clearlydemonstrates proof of concept for 2,5-disubstituted amide complexes asolefin polymerization catalysts.

MMAO Cocatalyst Temp, C. micromolesZr Activity I2 I21 MFR BBF 85 10.05,106 0.232 65.39 281 14.0 85 1.0 8,471 4.16 257 61.64 15.08 65 1.036,235 0.268 19.62 73.23 14.3

Reaction Conditions: 85° C., 600 mL hexane, 43 mL 1-hexene, MMAO,MMAO/Zr=1,000.

As mentioned above the 1H-nmr analysis was 45%pyridylamidepyrrole-zirconiumtribenzyl complex plus 55%tetrabenzylzirconium. The tetrabenzylzirconium was apparently employedin excess over ligand. Hence 10.0 micromoles probably translates to 4.5micromoles of pyridylamidepyrrolezirconiumtribenzyl complex.

In essence the true activities are likely a little more than doublethose shown in the table above.

Synthesis of N-amino-2,5-dimethylpyrrole

General procedure: N-aminophthalimide (5.35 g), acetonyl acetone (3.77g) and acetic acid (60 mL) were combined in a flask equipped with a stirbar. A cold water condenser was attached and the reaction mixture wasrefluxed for 2 hrs. The reaction mixture was allowed to cool to roomtemperature and filtered. The collected solids were dried in a vacuumoven. The filtrate was mixed with water then extracted with methylenechloride. The extracts were washed with water, dried and vacuumstripped. Both samples were analyzed by ¹H NMR and appeared to besubstantially the same compound.

Hydrazine (27.9 mmol, 0.89 g) was added dropwise to a solution of theabove product (27.9 mmol, 6.7 g) in ethanol. The reaction was heated toreflux for 0.5 hours. Some of the product precipitated during thereaction. Addition of acetic acid completed the precipitation. Thesolids were collected by filtration. Water was added to the filtrate andneutralized with Na₂CO₃. Excess ammonia added and the mixture wasextracted with ether. The extracts were vacuum stripped to a residue.

Reference: Flitsch, W., Kamer, U., Zimmermann, H.; Chem. Ber. 1969, 102,3268–3276.

Reaction of N-1-Amino-2,5-Dimethyl pyrrole with 2-Acetylpyridine

General procedure: The above N1-amino-2,5-dimethylpyrrole (31.1 mmol,3.42 g) was dissolved in benzene. 2-Acetylpyridine (31.1 mmol, 3.76 g)and hydrochloric acid (0.11 g, [1.0M solution in ether] were added. Thereaction was allowed to stir for 3 hours. The reaction was washed withwater, extract with ether, washed with brine. The extracts were vacuumstripped to isolate the product.

Alkylation of 2-Acetylpyridine, (N-1-Amino-2,5-Dimethyl pyrrole)imine

General procedure: The 2-acetylpyridine, (N-1-amino-2,5-dimethylpyrrole)imine (4.87 g) was dissolved in Benzene and chilled to 0° C.Trimethyl aluminum (1 equivalent) was added dropwise. The reaction wasallowed to slowly warm to room temperature. When complete the reactionwas transferred in stirring KOH/H₂O, extracted with ether and vacuumstripped to a liquid residue.

Reaction of Alkylated 2-Acetylpyridine, (N-1-Amino-2,5-Dimethyl pyrrole)imine with Tetrabenzyl zirconium

General procedure: In dry the box tetrabenzyl zirconium (0.200 mmol,0.091 g) was charged to a 7 mL amber bottle equipped with a stir bar andcap. Benzene-d₆ (1.5 mL) was added and stirred to dissolve. To a vialwas charged the amine derived from methylation of 2-acetylpyridine,(N-1-amino-2,5-dimethyl pyrrole) imine (0.200 mmol, 0.046 g) and 1.5 mLBenzene-d₆. The ligand solution was transferred into the tetrabenzylzirconium solution. The reaction was allowed to stir at room temperatureovernight.

MMAO Cocatalyst Temp, ° C. micromolesZr Activity I2 I21 MFR BBF Mn MwPDI 85 0.5 30,588 0.839 35.77 42.62 17.38 25,951 161,063 6.21 ReactionConditions: 85° C., 600 mL hexane, 43 mL 1-hexene, MMAO, MMAO/Zr =1,000.

Synthesis of 2-Acetylpyridine(1-Amino-cis-2,6-dimethyl piperidine)

General procedure: 2-Acetylpyridine (100 mmol, 12.1 g) was charged to a100 mL Schlenk flask equipped with a stir bar and septum. Hydrochloricacid (4.0 mmol, 4.0 mL, {1.0M solution in ether]) was added under aNitrogen purge. 1-amino-cis-2,6-dimethyl piperidine (80 mmol, 9.9 g,)was added to the reaction flask. A Dean-Stark apparatus was attached andthe reaction vessel was heated to 105° C. while under a nitrogen sweep.After one hour the Dean-Stark apparatus was replaced with a short pathdistillation head. One fraction was collected from the reaction.

Alkylation of 2-Acetylpyridine(1-Amino-cis-2,6-dimethyl piperidine)

General procedure: 2-acetylpyridine(1-amino-cis-2,6-dimethylpiperidine)imine (20 mmol, 4.6 g) and 10 mL toluene were charged to a 50mL Schlenk flask equipped with a stir bar and septum. The reactionvessel was chilled to 0° C. Trimethyl aluminum (63 mmol, 31.5 mL, [2.0Msolution in toluene]) was added dropwise. The reaction was allowed toslowly warm to room temperature. When the reaction was complete thesolution was transferred into a stirring solution of sodium hydroxideand water, extracted with toluene. The extracts were dried over MgSO₄and filtered. The filtrate was vacuum stripped to 4 g of amber liquid.Analysis by gas chromatography and ¹H NMR in Benzene-d₆ indicatedapproximate 80% conversion.

Reaction of the Amine derived from Alkylation of2-Acetylpyridine(1-Amino-cis-2,6-dimethyl piperidine)imine withTetrabenzyl zirconium

General procedure: In dry the box tetrabenzyl zirconium (0.200 mmol,0.091 g,) was charged to a 7 mL amber bottle equipped with a stir barand cap. Benzene-d₆ (1.5 mL) was added and stirred to dissolve. To avial was charged the Amine derived from alkylation of2-acetylpyridine(1-amino-cis-2,6-dimethyl piperidine)imine (0.200 mmol,0.050 g) and 1.5 mL Benzene-d₆. The ligand solution was transferred intothe tetrabenzyl zirconium solution. The reaction was allowed to stir atroom temperature overnight.

Polymerization activity with these dimethylcarbon-bridged catalysts washigher than for the corresponding methylbenzylcarbon-bridged catalysts.Comonomer incorporation was similarly low. Molecular weight againappears to surprisingly decrease at lower zirconium concentrations.

MMAO Cocatalyst, 2.0 micromoles MMAO/Zr = 1,000 Activity I2 I21 MFR BBF45,059 0.132 9.88 74.52 2.55 Conditions: 85° C., 85 psi ethylene, 43 mLhexene, no hydrogen.

MMAO Cocatalyst, 0.5 micromoles MMAO/Zr = 1,000 Activity I2 I21 MFR BBF34,353 4.49 111 24.72 3.22 Conditions: 85° C., 85 psi ethylene, 43 mLhexene, no hydrogen.

Polymerization activity with these dimethylcarbon-bridged catalysts washigher than for the corresponding methylbenzylcarbon-bridged catalysts.Comonomer incorporation was similarly low. Molecular weight againappears to surprisingly decrease at lower zirconium concentrations. Onenormally encounters lower molecular weights at higher aluminumconcentrations due to polymer chain-transfer to aluminum. The resultsare contrary to that here.

Size Exclusion Chromatography (SEC) anaylsis demonstrated that bimodaldistributions are possible with this catalyst system. Interestingly, byincreasing the zirconium and aluminum concentrations (2.0 micromoles Zrvs 0.5 micromoles Zr and 2,000 micromoles MMAO vs 500 micromoles MMAO) abimodal distribution was achieved. The results are illustrated in theFigure hereto.

Reaction of 2-Acetylpyridine(1-Amino-cis-2,6-dimethyl piperidine)iminewith Tetrabenzyl zirconium

General procedure: In dry the box tetrabenzyl zirconium (0.200 mmol,0.091 g) was charged to a 7 mL amber bottle equipped with a stir bar andcap. Benzene-d₆ (1.5 mL) was added and stirred to dissolve. To a vialwas charged 2-acetylpyridine(1-amino-cis-2,6-dimethyl piperidine)imine(0.200 mmol, 0.046 g) and 1.5 mL Benzene-d₆. The ligand solution wastransferred into the tetrabenzyl zirconium solution. The reaction wasallowed to stir at room temperature overnight.

Good polymerization activity was observed at 85° C.

MMAO Cocatalyst, 2.0 micromoles MMAO/Zr = 1,000 Activity I2 I21 MFR BBF26,824 1.60 159.0 99.65 2.05 Conditions: 85° C., 85 psi ethylene, 43 mLhexene, no hydrogen.Good polymerization activity was observed at 85° C.

MMAO Cocatalyst, 2.0 micromoles MMAO/Zr = 1,000 Activity I2 I21 MFR BBF26,824 1.60 159.0 99.65 2.05 Conditions: 85° C., 85 psi ethylene, 43 mLhexene, no hydrogen.

It is noteworthy that this 85° C. activity is much higher than for thecorresponding 2,5-dimethylpyrrole-amide complex documented earlier. The2,6-dimethylpiperidine derivative apparently has better thermalstability than this system.

Polymerizations using 0.5 micromoles of zirconium complex at varioustemperatures.

MMAO Cocatalyst, 0.5 micromoles MMAO/Zr = 1,000 T, ° C. Activity I2 I21MFR BBF 85 19294 87.43 20K 229 3.00 85 18,353 27.79 167 6.02 4.06 8519,294 21.95 103 4.69 2.74 75 18,824 1.94 47.03 24.28 2.88 95 7,059 — —— — 105 2,353 — — — — Conditions: 85° C., 85 psi ethylene, 43 mL hexene,no hydrogen.

1. A polymerization process comprising combining in a reactor olefins of2 to 30 carbon atoms with a catalyst composition, the catalystcomposition comprised of: a) a catalyst precursor represented by one ofthe formulae selected from the group consisting of:

where a is 1; T is a chemical moiety having 1 to 100 atoms, or hydrogen;M is an element selected from Groups 3 to 7 of the Periodic Table of theElements; Z is a coordination ligand; each L is a monovalent, bivalent,or trivalent anionic ligand; n is an integer from 1 to 6; m is aninteger from 0 to 5; Y is nitrogen; J is nitrogen; wherein the ring towhich J is part of is a five or six member ring; R can be independentlyhydrogen, or a non-bulky or a bulky substituent; and b is an integerfrom 0 to 20; and b) an activating cocatalyst wherein T is selectedfrom:

wherein Y is shown for convenience.
 2. The process of claim 1, wherein Zis selected from the group consisting of at least one oftriphenylphosphine, tris(C₁–C₆ alkyl) phosphine, tricycloalkylphosphine, diphenyl alkyl phosphine, dialkyl phenyl phosphine,trialkylamine, arylamine, a substituted or unsubstituted C₂ to C₂₀alkene, an ester an amine an di(C₁ to C₃)alkyl ether, an η⁴ diene,tetrahydrofuran, and a nitrile.
 3. The process of claim 1, wherein eachL is an anionic ligand independently selected from the group consistingof those containing up to 50 non-hydrogen atoms and selected from thegroup consisting of halogen containing groups; hydrogen; alkyl; aryl;alkenyl; alkylaryl; arylalkyl; hydrocarboxy; amides, phosphides;sulfides; silyalkyls; diketones; borohydrides; and carboxylates.
 4. Theprocess of claim 1, wherein each L is an anionic ligand independentlyselected from the group consisting of those containing from about 1 to20 non-hydrogen atoms and selected from the alkyl, arylalkyl, andhalogen containing groups.
 5. The process of claim 1, wherein M isselected from the group consisting of Hf and Zr.
 6. The process of claim1, wherein R is a non-bulky substituent selected from the groupconsisting of straight and branched chain alkyl groups.
 7. The processof claim 6, wherein R is a C₁ to C₁₀ straight chain alkyl group.
 8. Theprocess of claim 1, wherein R is a bulky substituent containing fromabout 3 to 50 non-hydrogen atoms and is selected from the groupconsisting of alkyl, alkenyl, cycloalkyl, heterocyclic (both heteroalkyland heteroaryl), alkylaryl, arylalkyl, polymeric, and inorganic ringmoieties.
 9. The process of claim 1, wherein R contains from about 4 to20 non-hydrogen atoms.
 10. The process of claim 1, further comprising asupport material.
 11. The process of claim 1, wherein the cocatalystcomprises aluminum; and wherein increasing the metallic element M andaluminum concentrations in the reactor increases the polyolefinbimodality.
 12. The process of claim 1, wherein a polyolefin isisolated, the process characterized in that as the concentration ofmetallic element M in the reactor decreases, the molecular weight of thepolyolefin decreases.